DE4206536A1 - DIRECT PURPOSES FOR FIBERS OF NATURAL ORIGIN AND SYNTHETIC FIBERS - Google Patents

Abstract

A new process is disclosed for preparing N-(2-nitro-4-aminophenyl)-aminoalkane sulfonic acids having formula (I), in which R<1>, R<2> and R<3> stand for hydrogen, alkyl groups with 1 to 4 C atoms or hydroxyalkyl groups with 2 to 4 C atoms and n is an integer from 1 to 6. Also disclosed are the salts of these compounds and their use as colouring agents for natural and synthetic fibres. They are preferably used for dyeing keratin-containing fibres, above all human hair.

Description

The invention relates to a process for the preparation of N- (2-nitro-4-aminophenyl) -aminoalkanesulfonic acids and their Ver Use for dyeing fibers of natural origin and synthe table fibers.

The substantive dyes play a part in dyeing prominent role. Direct dyes are water-soluble Compounds consisting of an aqueous solution or a Apply water-containing preparation to the fiber. You have to over have two important structural features: a chromophore system and one or more hydrophilic groups giving them one imparting water solubility.

In the class of nitro dyes are those of importance those on an aromatic system next to one or more nitro groups carry hydroxyl or amino groups; this combination Nitro substituents and electron-rich groups is for the Far responsibility of the compounds.

Sufficient water solubility is by substitution with reached polar groups. Preferably, the sulfonic acid or  Sulfonate used, while the sulfonic acid is in general tied directly to the aromatics. The resulting Benzenesulfonic acid derivatives differ from the Phenylalkanesulfonic acids and phenylaminoalkanesulfonic acids thereby, that in the latter the solubilizing group via alkyl or Aminoalkyl is attached to the aromatics.

For dyeing hair and furs are in the German design DE 11 14 775 already N- (nitro-4-aminophenyl) aminoalkane sulfonic acids and their salts are described. The thus obtained Fär However, exercises are not very intense in color. Besides, the Ver drive for the preparation of the compounds described there gravie denden disadvantages: According to this method is nitroparaphenylenediamine in benzene with propanesultone to N- (nitro-4-aminophenyl) -3-amino-1-pro implemented pansulfonic acid. On the use of carcinogenic Che Benzene and Propanesultone should be classified according to current knowledge However, if possible be dispensed with. Another disadvantage of this Synthesis principle is that the extension of the alkanesulfone acid chain limits are set, since the higher homologous alkane sultones are no longer easily accessible. Furthermore, according to this Verfah a mixture of isomers obtained predominantly N- (3-nitro-4-ami nophenyl) -3-amino-1-propanesulfonic acid. The 3-nitro isomer However, this leads only to unsatisfactory staining results. also are iso for today's more stringent toxicological tests merenreine products required.

The object of the invention is therefore to provide a process for the preparation the colorant suitable N- (2-nitro-4-aminophenyl) -aminoal Kansulfonsäuren without the disadvantages described above.  

A process for the preparation of N- (2-nitro-4-amino phenyl) -aminoalkanesulfonic acids of the formula I found

where R ¹ , R ² and R ^{3 are} hydrogen, alkyl groups having 1 to 4 C atoms or hydroxyalkyl groups having 2 to 4 C atoms and n is an integer from 1 to 6 and their salts by reacting compounds of the formula II

with compounds of the formula III,

R³N (H) - (CH₂) _n -SO₃H (III),

where R ¹ and R ² in formula II or R ³ and n in formula III have the same meaning as in formula I.

Preferably used is the method when in formula I, II and III R ¹ and R ^{2 is} hydrogen, R ^{3 is} hydrogen or methyl and n is 2 or 3.

Among the water-soluble salts are primarily the salts strong bases, such as the alkali metal salts, e.g. As the sodium or Potassium salt, or to understand the ammonium salts.

Preferably, the reaction mixture to neutralize at the reaction liberated hydrofluoric acid a basic Connection, z. As soda or potash added.

The process of the invention may be based on the use of highly toxic or carcinogenic compounds are dispensed with. The Compounds of formula I are easily precipitated or eliminated crystallize out of the reaction mixture in high purity ent hold. Only the 2-nitro isomers are formed. The Demand for isomerically pure products is thus taken into account In addition, according to the method of the invention is the way Compounds of the formula I with alkanesulfonic acid chains with more than 4 C atoms open.

As solvents, all common organic solvents are used, but preferably high-boiling Lö agent, such as. As dimethyl sulfoxide, used or what ser.

The N- (2-nitro-4-aminophenyl) -aminoalkanesulfonic acids of the formula I and their salts are excellent for dyeing fibers na of natural origin and synthetic fibers.  

According to the invention are among fibers of natural origin man Lichen, animal and vegetable fibers, such as silk, cotton, Linen, jute and sisal and keratin fibers, such as hair, furs, wool or feathers but also regenerated or modified natural fibers, such as As viscose, nitro and acetyl cellulose, alkyl, hydroxyal to understand kyl and carboxyalkyl celluloses. From the class of synthetic fibers are z. As polyamide, polyester, polyacrylic nitrile and polyurethane fiber.

Another object of the invention is therefore the use of N- (2-nitro-4-aminophenyl) -aminoalkanesulfonic acids of the formula I and their salts for dyeing fibers of natural origin and syn thetic fibers. The compounds of the formula I are termed di used direct dyes. Textile fibers are preferred after the exhaust process from an aqueous, for better solubility the compounds of formula I preferably set alkaline Dyeing liquor dyed at temperatures above 90 ° C.

The best staining results are achieved with keratin fibers. Wool, for example, comes in intense shades of camel brown dyed to reddish brown.

Another important in the dyeing keratin fiber is the human hair. Even human hair can with the verbin compounds of formula I already at physiologically beneficial tempera intensively colored below 40 ° C.

Another object of the invention is therefore the use of N- (2-nitro-4-aminophenyl) -aminoalkanesulfonic acids of the formula I and their salts for dyeing keratin-containing fibers, preferably human hair.  

For dyeing human hair, the compounds of Formula I in an aqueous cosmetic carrier, for. In creams, Emulsions, gels or surfactant, foaming solutions, eg. In Shampoos, foam aerosols or other preparations intended for Application on the hair are suitable, incorporated.

Usual components of such cosmetic preparations are, for. B. Wetting and emulsifying agents, such as anionic, nonionic or ampholytic surfactants, e.g. Fatty alcohol sulfates, alkanesulfonates, α-olefinsulfonates, fatty alcohol polyglycol ether sulfates, Ethylenoxidauflagerungsprodukte of fatty alcohols, fatty acids and Alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, Fatty acid alkanolamides and thickeners, such as. Methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, Fatty acids, perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, Pantothenic acid and cholesterol. The ingredients of the cosmetic Carriers are used to make hair dyes for these Used for customary amounts. For example, emulsifiers are used in Concentrations of 0.5 to 30 wt .-% and thickener in Concentrations of from 0.1% to 25% by weight of the total colorant used. For use in hair dyes, the substantive dyes of the formula I in an amount of 0.01 to 5 wt .-%, preferably from 0.1 to 2 wt .-%, based on the total Preparation, used.

The dyeing temperatures in this case are considerably lower than in textile dyeing. They should not exceed 40 ° C. With The hair colorations obtained in the compounds of the formula I are in the Range from camel brown to pinkish and different clearly from that in the German patent application DE 11 14 775 be written light brown shade. They also have high levels Color intensities, light and wash fastness.  

For color modification, the compounds of formula I with üb used in combination known substantive direct dyes become. In addition, well-known Oxidation hair dye precursors may be included. If that hair dye according to the invention oxidation dye precursors contains, it is also advisable to add a small amount a reducing agent, e.g. B. from 0.5 to 2 wt .-% sodium sulfite for the stabilization of the oxidation dye precursors. In this Case, this is with a prior to applying the hair dye Oxidizing agent is added to the oxidative evolution of Initiate oxidation dye precursors. As oxidizing agent in particular hydrogen peroxide or its Addition products of urea, melamine or sodium borate and Mixtures of such hydrogen peroxide addition products with Potassium peroxide sulfate in question.

The application of the hair dye can be independent of the type of hair cosmetic preparation, e.g. As a cream, gel or shampoo, im slightly acidic, neutral or alkaline medium. before zugt is the application of the hair dye in a pH range of 6 to 10.

The following examples are intended to illustrate the subject matter of the invention but without limiting it.  

Examples Preparation Examples 1. N- (2-nitro-4-aminophenyl) -2-amino-1-ethanesulfonic acid (F1)

A mixture consisting of 12.5 g (0.1 mol) of 2-amino-1-ethanesulfonic acid (taurine) and 6.9 g (0.05 mol) of potassium carbonate in 20 ml of dimethyl sulfoxide was heated to 110 ° C he. A solution of 7.8 g (0.05 mol) of 4-fluoro-3-nitroaniline in 20 ml of dimethyl sulfoxide was added dropwise at this temperature within 90 minutes. After cooling, the reaction mixture was poured into 400 ml of water. The solution was adjusted to pH 3 with dilute hydrochloric acid. After cooling, the product was filtered off with suction, washed with water and dried in vacuo at 60 ° C.
Yield: 6.35 g (48.7% of theory)
A UV / VIS spectrum was recorded in ethanol as solvent, containing 1% 10% ammonia: λ _max = 247 nm, 294 nm.

2. N- (2-nitro-4-aminophenyl) -3-amino-1-propanesulfonic acid (F2)

A mixture consisting of 3.9 g (0.025 mol) of 4-Flu or-3-nitroaniline and 3.8 g (0.025 mol) 3 Amino-1-propanesulfonic acid and 10.4 g (0.075 mol) of potassium carbonate in 40 ml of water was refluxed for 5 hours. After cooling, it was brought to pH 2 with concentrated hydrochloric acid set. The product was filtered off with suction, nachgewa with water and dried in vacuo at 60 ° C.  

Black crystals were obtained.
Yield: 1.85 g (26.8% of theory)
A UV / VIS spectrum was recorded in ethanol as solvent, containing 1% 10% ammonia: λ _max = 247 nm, 486 nm.

3. N- (2-nitro-4-aminophenyl) -2-methylamino-1-ethanesulfonic acid (F3)

The synthesis was carried out analogously to Example 2, but with 2-methylamino-1-ethanesulfonic acid (N-methyltaurine) instead of 3-amino-1-propanesulfonic acid. This gave gold-shining crystals.
Yield: 5.6 g (81.3% of theory)

applications Dyeing textile fibers

The stains were on a multi-fiber conjugate tissue, type DW (German Authenticity Commission) of Beuth-Verlags-GmbH, Cologne, be consisting of 6 textile strips made of acetylcellulose fibers (2,5 Acetyl groups per monomer unit), cotton fibers, polyamide fibers, Polyester fibers, polyacrylic fibers and wool fibers performed.

0.5 g of the dye, 8 g of sodium sulfate saccharide and 2 g Sodium carbonate was dissolved at 60 ° C in 100 ml of water. The Farmer The multi-fiber conjugated fabric was added to the bath. Subsequently was heated to 48 ° C within 45 minutes. This temperature was maintained for 1 hour using evaporated water  was replaced continuously. The dyed material was on closing the dyebath and removed first cold and then hot rinsed. The dyed multifilament fabric was then in for 20 minutes a mixture of 250 ml of water and 0.25 g of sodium lauryl sulfate cooked. The fabric was then rinsed and dried. The Tints obtained with dyes 1 to 3 are given in Table 1 remove.

Table 1

Dyeing of human hair

Hair dye creams of the following composition were prepared provides:

Fatty alcohol C _12-18 | 10 g Fatty alcohol C _12-14 + EO sulfate, Na salt (28%) 25 g water 60 g direct dye (F1 to F3) 7.5 mmol ammonium sulfate 1 g conc. ammonia solution to pH 9.5 water ad 100 g

The ingredients were mixed together in order. To Addition of substantive dyes was treated with conc. Ammoniaklö Adjust the pH of the emulsion to 9.5. Then was with Water made up to 100 g. The coloring cream was about 5 cm long strands standardized, 90% gray, but not be especially pretreated human hair applied and there 30 minutes leave at 27 ° C. After completion of the dyeing process was rinsed the hair, washed out with a standard shampoo and then dried. The results of the dyeing tests are Table 2.  

dye Nuance of dyed hair F1 pink F2 dull red F3 camel brown

Claims (4)

1. A process for the preparation of N- (2-nitro-4-aminophenyl) aminoalkanesulfonic acids of the formula I. wherein R ¹ , R ² and R ^{3 are} hydrogen, alkyl groups having 1 to 4 carbon atoms or hydroxyalkyl groups having 2 to 4 carbon atoms and n is an integer from 1 to 6 and their salts by reacting compounds of formula II with compounds of the formula IIIR³N (H) - (CH₂) _n -SO₃H (III), where R ¹ and R ² in formula II or R ³ and n in formula III have the same meaning as in formula I. 2. The method according to claim 1, wherein in formula I, II and III R ¹ and R ^{2 is} hydrogen, R ^{3 is} hydrogen or methyl and n = 2 or 3. 3. Use of N- (2-nitro-4-aminophenyl) aminoalkanesulfonic acids of the formula I and their salts for dyeing fibers natural Origin and synthetic fibers. 4. Use of N- (2-nitro-4-aminophenyl) -aminoalkanesulfonic acids of the formula I and their salts according to claim 3 for dyeing keratin-containing fibers, preferably human hair.